Photochemical Method For Producing Hydrocarbons

ABSTRACT

The present invention relates to a method of using radiation and (in one embodiment) solar energy and UV radiation to convert natural products, for example derivatives of vegetable oils, to lower molecular weight hydrocarbons. The invention further relates to a process whereby these hydrocarbons can be converted to vinyl monomers and used in the formation of plastics, solvents, fuels and the like.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.11/540,906, filed Sep. 29, 2006, which claims the benefit of U.S.Provisional Application No. 60/723,286, filed Oct. 3, 2005.

DEFINITIONS

Fatty acid—any of the several long alkyl chain acids found in essentialoils. A table of those identified from a variety of sources isreproduced.

Alkanone—ketone with two aliphatic groups.

Fatty ketone—a ketone with aliphatic groups one or both of which is froman alkyl or alkenyl group of the type typically found in fatty acids.

Aryl fatty ketone—a ketone with one aryl and one alkyl or alkenyl groupand, more particularly and alkyl or alkenyl group of the type generallyfound in fatty acids.

Phenone—generic phenyl alkyl ketones.

n-π* transition—a photophysical term describing an electronic transitioncaused by the absorption of light of a specific wavelength; transitioninvolves, in the context used here, the carbonyl group.

π-π* transition—a photophysical term describing an electronic transitioncaused by the absorption of light of a specific wavelength; transitioninvolves any unsaturated function.

UV-A—light of wavelengths 320-400 nm.

UV-B—light of 270-320 nm.

UV-C—light of shorter wavelengths than 270 nm.

Norrish Type II Reaction—Term that refers to the photochemically inducedsplit of a ketone or ester into two smaller parts one of which is anunsaturated hydrocarbon. Examples of the synthetic use of certainNorrish Type II reactions can be found Kellogg, R. M.; Prins, W. L.;Schoustra, B. M.; Neckers, D. C. Developmental Photochemistry. TheNorrish Type II Reaction. J. Org. Chem. 1971, 36, 1838-184.

Aryl—includes phenyl groups that may be unsubstituted, mono-, di-, andtri-substituted, C₆H_(5-n)R_(n) where R_(n)=R₁, R₂, R₃. R₄, R₅ which arethe same or different. R_(n) may be H, linear or branched alkyl[C_(m)H_(2m+1) where m=1-25], alkenyl [C_(m)H_(2m−1) where m=1-25]cycloalkyl [C_(m)H_(2m−1) where m=1-25], alkynyl [C_(m)H_(2m−3) wherem=1-25], mono, di, or poly substituted naphthyl C₁₀H_(8-n)R_(n), mono,di, or poly substituted anthryl C₁₄H_(10-n)R_(n), mono, di or polysubstituted phenanthryl C₁₄H_(10-n)R_(n), polycondensed aromatic,C₁₆H₁₀R_(n) and the like; R_(n) may also be hydroxy, ether [O—R₆ whereR₆ is linear or branched alkyl [C_(m)H_(2m−1) where m=1-25], alkenyl[C_(m)H_(2m−1) where m=1-25], cycloalkyl [C_(m)H_(2m−1) where m=1-25],alkynyl [C_(m)H_(2m−3) where m=1-25], mono-, di-, and tri-substituted,C₆H_(5-n)R_(n), mono, di, or poly substituted naphthyl C₁₀H_(8-n)R_(n),mono, di, or poly substituted anthryl C₁₄H_(10-n)R_(n), mono, di or polysubstituted phenanthryl C₁₄H_(10-n)R_(n), polycondensed aromatic,C₁₆H₁₀R_(n) and the like, F, Cl, Br, I, C_(m)H_(2m+2−x)M_(x) where M=F,Cl, Br, I, and x=1-25, thiophenol, thioether [S—R₆ where R₆ is linear orbranched alkyl [C_(m)H_(2m+1) where m=1-25], cycloalkyl [C_(m)H_(2m−1)where m=1-25] alkenyl [C_(m)H_(2m−1) where m=1-25], cycloalkyl[C_(m)H_(2m−1) where m=1-25] alkynyl [C_(m)H_(2m−3) where m=1-25],mono-, di-, and tri-substituted, C₆H_(5-n)R_(n), mono, di, or polysubstituted naphthyl C₁₀H_(8-n)R_(n), mono, di, or poly substitutedanthryl C₁₄H_(10-n)R_(n), mono, di or poly substituted phenanthrylC₁₄H_(10-n)R_(n), polycondensed aromatic, C₁₆H₁₀R_(n) and the like,amino [NR₇R₈ where R₇ and R₈ are the same or different and are H orlinear or branched alkyl [C_(m)H_(2m+1) where m=1-25], cycloalkyl[C_(m)H_(2m−1) where m=1-25] alkenyl [C_(m)H_(2m−1) where m=1-25],alkynyl [C_(m)H_(2m−3) where m=1-25], mono-, di-, and tri-substituted,C₆H_(5-n)R_(n), mono, di, or poly substituted naphthyl C₁₀H_(8-n)R_(n),mono, di, or poly substituted anthryl C₁₄H_(10-n)R_(n), mono, di or polysubstituted phenanthryl C₁₄H_(10-n)R_(n), polycondensed aromatic,C₁₆H₁₀R_(n) and the like, piperidino, morpholino, pyrryl, ammonium, [NR₄⁺], amido [—NR₂C(═O)—], ester, [—COOR_(n)], sulfonamide [—SONR₂],aldehyde —[CHO], ketone [—C(═O)R] one or more heterocyclic groups thatmay or may not be alkylated including thiophene, furan, indole,benzo[b]thiophene, benzo[c]thiophene, benzo[b]furan, benzo[c]furan,indole, heterocyclic groups with two or more heteroatoms, and the like.The group might also consist of substituent(s) (C1-C10)alkyl, acryloxy,methacryloxy, chloro and fluoro. R_(n) may also be polymeric includingpoly(ethylene), poly(isopropenyl), poly(propylene), poly(butadienyl),poly(styryl), poly(acylate), poly(methacrylate), poly(fluorocarbon),poly(chlorocarbon) and the like.

Natural oil—Any oil derived from a naturally grown crop particularlypeanut, soybean, corn, sunflower, tung, canola, cotton, coconut,so-called vegetable oils, and the like.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention involves a method that uses radiation andparticularly solar energy or UV (photochemical) induced processes toconvert derivatives of vegetable oils to useful products. In oneembodiment, the invention provides a process for converting fatty acidesters or their derivatives to hydrocarbons such as alkenes, dienes,trienes and the like. In a more particular embodiment the inventionrelates to photochemical methods that convert long chain fatty acids toolefins, dienes and trienes that can, if necessary, be further refined,cracked, reformed or converted to vinyl monomers, halogenatedhydrocarbons and other commercial products. In a still more particularembodiment, a method is provided for forming ketones (e.g., fattyketones) and converting them to olefins by exposing them to radiation.

2. Background

Fossil fuels, specifically products refined from petroleum, remain theprincipal source of hydrocarbon feed stocks. In addition to being usedas a source of gasoline and other fuels, said hydrocarbons are alsoconverted, or used directly, to form the starting materials from whencemost synthetically made plastics and commercial solvents are obtained.Thus critical monomers such as styrene, butadiene, acrylic acid,propylene, ethylene and tetrafluoroethylene are currently obtained aseither direct cracking products of crude oil or derived from directcracking products of crude oil. Critical solvents like naphtha, hexanes,petroleum ether, methylene chloride, chloroform, carbon tetrachlorideand the like, also are all either directly obtained, or produced, frompetroleum. As the supply of fossil fuels, particularly crude oil,dwindles, and as other nations in the world compete for the productsderived from oil the costs of raw materials for commercial plastics willincrease, supplies will become harder to get and fossil fuel sourceswill be unable to meet demand.

A series of reports document that a shortage of petroleum products asderived from fossil fuels is anticipated. (Nathan Lewis, ChemicalChallenges in Renewable Energy, Cal Tech publication, 2004 incorporated,by this citation, herein). In anticipation of the expected shortages newsources of energy are continually being evaluated and proposed. Thisapplication focuses on another facet of the problem, namely, that newsources of raw hydrocarbon feedstocks alternative to petroleum must bedeveloped. Though land is unlikely to have the potential of meeting theneeds of the global energy demand through the production of biofuelsbecause the area that would need to be cultivated for such purposes isnearly equivalent to the area now under cultivation world-wide, andbiomass conversion to power isn't that efficient anyway (see Lewis, opcit), the use of biomass to produce the raw materials from whenceplastics are derived is a much less imposing challenge, and obviouslywithin reach of experimental developments in the chemical sciences usingthe sun.

A relatively few molecules produced by thermal decomposition (cracking)products of petroleum, unsaturated hydrocarbons mostly, form the basisof most of the commercial plastics industry. These include: ethylene(CH₂═CH₂), propylene (CH₃CH═CH₂), styrene (C₆H₅CH═CH₂) and butadiene(CH₂═CH—CH═CH₂). Of these propylene is a particularly important startingmaterial because it is used to form acrylic acid, the base stock ofacrylates. Hydrocarbon solvents like petroleum ethers can be useddirectly from refined petroleum while halocarbon solvents like carbontetrachloride (CCl₄) and perchloroethylene (C₂Cl₄) are produced byhalogenation of methane and ethylene respectively.

In a recent report (Aug. 22, 2005, Energy Futures: Trends, Outlook andImplications) Don McConnell, CEO Batelle Lab Operations said “Bio-basedchemicals can provide a hedge to offset petroleum based polymers &“Bio-refineries” will first be developed from food processing capacity”.In accordance with one embodiment of this invention, the oils of commonvegetable crops are an alternative potential source of critical monomerssuch as propylene, ethylene, butadiene, styrene and acrylic acid. Thoughnone have been developed or exploited for same, certain vegetable cropscontain percentages of oil ranging from a few percent for corn to almost30% for crops like peanuts, and these oils, following chemical andphotochemical change, are a source of hydrocarbon feed stocks. Majorconstituents of these oils are derived from glycerol (CH₂OHCHOHCH₂OH) inthe form of long chain alkyl and alkenyl esters called glycerides. Theseare likely formed in nature, as they would be in the lab, by anesterification reaction involving reaction of a long alkyl or alkenylchain carboxylic acid with glycerol. Said long chain fatty acids whichinclude palmitic, stearic, oleic, linolenic and linoleic (and all of theacids derived from food oils—Table 12-2, C. R. Noller, OrganicChemistry, Saunders, 1965, page 209) are themselves, just one stepremoved from the raw materials of petroleum.

It has long been known that the oils and fats can be removed from thevegetable by extraction with hydrocarbon solvents such as hexanes orpetroleum ether, processed and converted to products that can be used infoods such as cooking oils, tofu and the like. However most grower'sorganizations, for example the soybean growers association, corn growersassociation, peanut growers association, etc. clearly recognize theycould find additional, uses of their crops in the industrial market andhave efforts that are more or less active to develop alternative (sicindustrial, as opposed to food) uses of their crops. Among the largestpotential of these is the formation from soya oil of a fuel known asBiodiesel. Biodiesel is defined as mono-alkyl esters of long chain fattyacids derived from vegetable oils or animal fats that conform to ASTMD6751 specifications for use in diesel engines. These mono-alkyl estersare mostly methyl esters that are made from the glycerides bytrans-esterification—the process of cooking the glycerides in thepresence of a catalyst with an excess of a low molecular weight alcohol,for example methyl alcohol. This produces glycerol as a side productwhich must be separated. Biodiesel refers to the pure fuel beforeblending with diesel fuel. Biodiesel blends are denoted as, “BXX” with“XX” representing the percentage of biodiesel contained in the blend(i.e.: B20 is 20% biodiesel, 80% petroleum diesel). In 2004,approximately 20 million gallons of biodiesel was produced by a group ofprocessors. This is far from capacity and expected to grow. Biodiesel ismade entirely from soy and its chemical composition is said to be in theform of the methyl esters of soy: (Source: National Biodiesel Board).

The essential fatty acids that are converted to methyl esters in theformation of Biodiesel are mainly the acids palmitic, stearic, oleic,linoleic and linolenic which are, in turn, the principle fatty acidsfound in most foodstuffs. Palmitic and stearic acid are the so-called“saturated acids” in that they are comprised of long hydrocarbon chainsof 15 and 17 carbons containing no double bonds. Saturated fatty acidesters are disadvantageous in foods so a number of growers organizationshave attempted to reduce their content in commercially grown cropseither by genetically engineering seeds to produce lower amounts ofsaturated oils, or by finding growing regions that already produce loweramounts of saturated oils and increasing production in these areas.Oleic, linoleic and linolenic acid, as well as others, are unsaturatedacids and therefore preferred in foods with oleic acid beingparticularly preferred. Typically, in the oil of soy, saturated acidsmake up from 10 to 20% of the mono, di- and tri-glyceride content whilethe remainder is a combination of 3 or more unsaturated acid glycerides.

The average molecular weight of soybean oil methyl esters is 292.2. Thiswas calculated using the average fatty acid distribution for soybeanmethyl esters below.

Typical Soybean Oil Methyl Ester Profile Fatty Acid Percent Wt. FormulaPalmitic 12.0 270.46 C₁₅H₃₁CO₂CH₃ Stearic 5.0 298.52 C₁₇H₃₅CO₂CH₃ Oleic25.0 296.50 C₁₇H₃₃CO₂CH₃ Linoleic 52.0 294.48CH₃(CH₂)₄CH═CHCH₂CH═CH(CH₂)₇ CO₂CH₃ Linolenic 6.0 292.46CH₃(CH₂CH═CH)₃(CH₂)₇ CO₂CH₃

Fatty acids themselves may be converted by chemical reaction topolymerizable monomers. An oxidized form of soya oil, so-calledepoxidized soya oil, is used as an additive in monomer mixtures fromwhence plastic coatings are made and formed. Polyesters are also derivedfrom dicarboxylic acids such as those that might be obtained from fattyacid feedstocks.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the invention a process is providedthat comprises converting fatty acids to the raw materials of plasticsthat would otherwise come from petroleum. In accordance with a furtherembodiment of the invention, the converting step includes radiating withsunlight or other artificial sources of light, for example, lamps. Infurther embodiments, the photodegradation products produced by suchsolar and photochemical processes are refined, cracked to smallermolecular parts, reformed to more useful and somewhat larger lowmolecular weight products, oxidized, and eventually converted to many ofthe low molecular weight monomeric unsaturated hydrocarbons (such asstyrene, ethylene, propylene, butadiene and the like) or derivativessuch as acrylic acid from whence acrylates can be formed and/orhalogenated to form haloethylenes such as vinyl chloride, vinyl bromide,vinyl fluoride, vinylidine chloride, vinylidine fluoride,tetrafluoroethylene, and the like.

A variety of ketones, esters and other derivatives of carboxylic acidscan be cracked by light from the sun or artificial sources to lowermolecular weight products. In particular organic compounds includingketones and esters undergo a cracking reaction that is known is in theart as the Norrish Type II reaction (see the Appendix) from whence theproducts are a lower molecular weight ketone (in the case of ketones),or an aldehyde (in the case of esters) and, in both cases, lowermolecular weight hydrocarbons specifically alkenes, dienes, trienes andthe like. In accordance with one embodiment of the invention, thesereactions are used in the solar cracking of fatty ketones tohydrocarbons. In accordance with one embodiment, vegetable oilconversion products are used as starting materials (without additionalprocessing) by one or more subsequent secondary activation step(s),photochemical degradation. Carboxylic acids are easily converted toketones as well as to esters and many different references teach thesynthetic steps to achieve such conversions. In particular, in oneembodiment, fatty acids are converted to fatty ketones by Friedel-Craftsreactions from fatty acid chlorides or anhydrides and the products ofsaid conversions are photodegraded.

In one aspect methods of decomposing a natural source of fatty acids orfatty acid derivatives into one or more hydrocarbons by directirradiation with light are disclosed. In one embodiment, the methodsinclude providing a natural source of fatty acids or fatty acidderivatives such as fatty acid esters, fatty acid amides, or a fattyalkanones and irradiating the natural source with UV-C light todecompose the fatty acids or fatty acid derivatives into one or morehydrocarbons.

In another embodiment, the methods include providing a natural source offatty acids or fatty acid derivatives such as fatty acid esters, fattyacid amides, or a fatty alkanones, adding an unreactive, light absorbingspecie thereto, and irradiating the natural source and unreactive, lightabsorbing specie directly with at least one of UV-A light and UV-Blight. The unreactive, light absorbing specie absorbs energy from theUV-A light and/or the UV-B light and transfers the energy, immediatelyafter light absorption, to the fatty acids or fatty acid derivatives todecompose the fatty acids or fatty acid derivatives into one or morehydrocarbons.

In another embodiment, the methods include providing a source ofpalmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid,or combinations thereof, or derivatives thereof, and irradiating thesource directly with UV-C light or adding an unreactive, light absorbingspecie that absorbs radiation of at least one of UV-A and UV-Bwavelengths and irradiating the source with at least one of UV-A lightand UV-B light. Either process decomposes the palmitic acid, stearicacid, oleic acid, linoleic acid, linolenic acid, or combinationsthereof, or derivatives thereof into one or more hydrocarbons.

In accordance with one embodiment, the esters of fatty acids such asthose derived from vegetable fats and oils by transesterification withalcohols can be expected to decompose by a Norrish Type II process whenexposed to short wavelength UV radiation. It is expected that esterscontaining aromatic groups will react at longer wavelengths of lightthan those in which the alcohol used in the trans-esterificationreaction is an alkanol. In accordance with one embodiment the methylesters of biodiesel are exposed to radiation with short wavelength lightdirectly.

In accordance with one embodiment, the hydrocarbons (alkenes, dienes,trienes and the like) derived from the Norrish Type II processes (above)are treated, refined, distilled and cracked much as the alkenes, dienes,trienes and the like derived from crude oil are refined, distilled andcracked, such that they can be used to form the raw materials forcommercial and industrial plastic formation.

In accordance with one embodiment, the alkenes, dienes, trienes and thelike derived from the Norrish Type II processes (above) are selectivelyoxidized such that acrylic acid is the eventual product. The subsequentreactions of photochemically produced terminal olefins with anhydroushydroperoxides in the presence of certain organometallic catalystsforming allylic hydroperoxides which can be subsequently cracked toacrylic acid is one such reaction and, as such, is described in Yu,J-Q.; Corey, E. J. Org. Letters 2002, 4 2727; Crich, D; Zou, Y; Org.Letters 2004, 6, 775; Catino, A. J.; Forslund, R. E.; Doyle, M. P. J.Amer. Chem. Soc. 2004, 126, 13622. There are others some of which areappended hereto.

DETAILED DESCRIPTION

One embodiment of the invention is a process comprising hydrolyzingvegetable oil glycerides to fatty acids or fatty acid esters, convertingthe fatty acid or ester to a light-sensitive compound such as a ketone,and exposing the light-sensitive derivative to radiation to form ahydrocarbon such as an olefin. In a particular embodiment, the fattyacid or ester is converted to an anhydride or acid chloride that isreacted with an aromatic compound in a Friedel-Crafts reaction toproduce an aryl alkyl ketone that is photoreactive. To convert theketone to the desired hydrocarbon products, the Norrish Type II reactionis used. In a particular embodiment, this takes the form of activatingthem to the phenones or to derivatives such as aromatic esters that aresusceptible to UV-A and UV-B wavelengths.

Conversion to an aromatic ketone (e.g., phenone) can be accomplished ina number of ways but most generally takes advantage of an electrophilicsubstitution reaction such as that referred to as a “Friedel-Crafts'reaction. In a common example of the Friedel Crafts reaction, anaromatic hydrocarbon such as benzene or toluene is added to a slurry ofa 2:1 mixture of the carboxylic acid derivative (anhydride or acidchloride) and anhydrous aluminum chloride in a non-reactive solvent suchas methylene chloride or carbon disulfide and a molar equivalent of thearomatic hydrocarbon is added and the mixture refluxed for a period.Subsequently the reaction mixture is poured into ice, extracted withhydrocarbon solvent and the subsequently formed solution neutralized bywashing with base, dried and the solvent distilled. The residue is thearomatic ketone or phenone.

This process is just one of the many ways in which a fatty acid or itsderivative can be converted in one step to an aryl alkyl ketone. Thereaction has been described in numerous reviews including that by Price,C. C. in Adams, R. Organic Reactions Vol III., John Wiley and Sons, NewYork, N.Y., 1946 P. 1, and that by Berliner, E.; Organic Reactions Vol.V, John Wiley and Sons, New York, N.Y., 1949 P. 229; as well as laterseries Friedel-Crafts and Related Reactions, George A. Olah,Interscience Publishers, 1964 and that by Patai, The Chemistry of theCarbonyl Group, Saul Patai, Editor, Interscience Publishers 1966.Details of specific preparations can be found in Allen and Barker,Organic Synthesis, Coll Vol II, 1943 156 and in Wagner, R. B.; Zook, H.B.; Synthetic Organic Chemistry, pp 316 ff, John Wiley & Sons, 1953. Thespecific preparation of stearophenone can be found in Seidel andEngelfried, Ber. 1936, 69B, 2578. Unsaturated ketones as wouldanticipated from oleic acid, linoleic acid and linolenic acid can alsobe achieved by this route as found in Darzens, Compte. Rendu 1940, 211435. It will be recognized that any of the fatty acids generated by thehydrolysis of typical vegetable oils will be susceptible, when convertedto an acid anhydride or acid chloride, to Friedel Crafts reactionconditions and it is our intention to cover all such cases. Suchreactions have been reported with ferrocene [Synthesis and redoxproperties of ferrocene derivatives containing an oleyl group. Butkus,Eugenius; Tauraite, Daiva; Barauskas, Justas; Talalkyle, Zita; Razumas,Valdemaras. Journal of Chemical Research, Synopses (1998), (11),722-723.] and with styrene Ralston, Anderson W.; Vander Wal, Robert J.Acyl styrenes. (1940), US 2197709 as well as with linoleyl andlinolenoyl chloride Ralston, A. W.; Vander Wal, R. J.; Bauer, S. T.;Segebrecht, E. W. Fatty-acyl-modified resins-dicyclopentadiene,coumarone and indene types. Journal of Industrial and EngineeringChemistry (Washington, D.C.) (1940), 32 99-101.

Many modifications of Friedel Crafts acylation reaction conditions areknown. As specific procedure, that used for the synthesis of a simplearyl alkyl ketone is illustrated below.

A mixture of 0.11 m [11.5 g] styrene, 0.11 m [15 g] AlCl₃ and 75 mlchlorobenzene was prepared and 30 g oleyl chloride added. The reactionwas stirred and heated to 40° for one hour and then poured onto ice.Linoleyl styrene, linolenyl styrene and lauroyl styrene were preparedsimilarly.

Other synthetic processes may also prove beneficial in the synthesis ofketones. One such is that reported oxidative rearrangements ofarylalkenes with [hydroxy(tosyloxy)iodo]benzene in 95% methanol: ageneral, regiospecific synthesis of α-aryl ketones. Justik, M. W.;Koser, G. F. Tetrahedron Letters 2004, 45, 6159-6163. Other methods ofadding photoreactive moieties to fatty acid derivatives that may be usedin other embodiments of the invention include those disclosed in J. Med.Chem. 1988, 31, 1052. and WO 2005 0553702.

Friedel Crafts reactions involving unsaturated acids and acidchlorides/anhydrides such as oleic acid and its derivatives, linoleicacid and its derivatives and linolenic acid and its derivatives mayproduce side products. A method to avoid this is to require ahydrogenation step in order to make the reaction more efficientsubsequently. Thus unsaturates are removed prior to the next acylationstep which produces the ketones. This has the effect of converting eachof the unsaturated fatty acids to stearic acid which is subsequentlyconverted to the ketone.

In accordance with a further embodiment, fatty acid alkanones, aliphaticketones can also be formed from fatty acids or their derivatives, andalso photochemically cracked by the Norrish Type II reaction with lightto alkenes and lower molecular weight ketones. Synthesis of alkanonesfrom acids is well known in the art. For example dehydration of theoctadecanoic acid to the form the ketene and/or dehydrochlorination ofthe acid chloride followed by ketene dimerization has been reported (US2369919 Sauer, J. C “Ketoethenones and Process Therefor”) to formoctadecanoylhesadecylethenone C₁₇H₃₃COC(C₁₆H₃₃)═C═O in high yield.However there are a number of other simple routes to alkyl fattyketones. The decarboylation of fatty acids over thoria at hightemperatures)(400-500° produces the symmetrical alkanone in nearquantitative yield. Thus octanoic acid, on decarboxylation produces8-pentadecanone. Higher molecular weight ketones can be synthesizedusing the same procedure from the methyl esters. For instancedi-n-undecylketone is prepared in 93% yield from lauric acid (Swann,Appel and Kistler, Ind. Eng. Chem. 1934, 26, 1014) and stearone(di-n-heptadecyl ketone) in 95% from stearic acid (Curtis, Dobson andHatt, J. Soc. Chem. Ind. London 1947, 66, 402). Unsaturated acid esters,for example, 9-undecenoic acid, ethyl ester give 80-90% yields of theketone (undecylenone). It is thus expected that oleic acid, linoleicacid and linolenic acid will dimerize under similar conditions to theappropriate ketone. The subsequent photoreactions of consequence arediscussed in detail in the various textbooks in photochemistry includingTurro, N.J. Molecular Photochemistry Mill Valley, Calif. 1991 andGilbert, A; Baggott, J. Essentials of Molecular Photochemistry, CRCPress 1984. In accordance with a further embodiment the degradationproducts, the olefins are treated, distilled, refined and the like, suchthat they can be used to form the raw materials for commercial andindustrial plastic formation.

Photochemical Reaction:

It will be recognized that there are numerous alternative possibilitiesfor carrying out synthetic scale photochemical processes (eg. Neckers,D. C. Continuous Oxidation Method. U.S. Pat. No. 4,849,076, Jul. 18,1989). The examples herein are cited to illustrate the principle only.It will also be recognized that optimization of these processes ispossible such that all of the acetophenone or analogous aromatic ketoneproduct is removed at the instant of formation. This expedient isparticularly useful. Many aromatic ketones are, themselves, commerciallyuseful as outlined in Appendix 2. It must also be recognized by thosefamiliar with the art that the ketone and other carbonyl groupcontaining products are themselves photoreactive and could be, as such,be further converted to aromatic alcohols and other compounds containingspecific functional groups in situ. Such subsequent reaction processesare also within the scope of this invention.

We include, as evidence of this recognition, a list of aromatic ketonesthat when incorporated (via Friedel Crafts or activating steps) intocrop fatty acids may confer Norrish Type II reactivity when irradiatedwith UV-A and UV-B light. These ketones include those prepared byFriedel Crafts reactions of benzene, toluene, o-, m- and p-xylene, ethylbenzene, o-methyl ethyl benzene, m-methyl ethyl benzene, p-methyl ethylbenzene, n-propylbenzene, o-methyl n-propyl benzene, m-methyl n-propylbenzene, p-methyl n-propyl benzene, isopropylbenzene, o-methyl isopropylbenzene, m-methyl isopropyl benzene, p-methyl isopropyl benzene, t-butylbenzene, o-. m- and p-methyl tert-butylbenzene, o-. m- and p-ethyltert-butyl benzene, o-. m- and p- n-propyl tert-butyl benzene, o-. m-and p-isopropyl tert-butyl benzene, o-. m- and p- n-butyl tert-butylbenzene, o-. m- and p-sec-butyl tert-butyl benzene, o-. m- andp-isobutyl tert-butyl benzene, m-di-tert-butylbenzene.p-di-tert-butylbenzene, 1,3,5-tri-tert-butylbenzene, and all otherappropriately substituted alkylbenzenes of 20 or less carbon atoms inthe alkyl chain. The list of reactive ketones that can be prepared byFriedel Crafts reactions also includes all ketones prepared from anisoleand methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butylbenzene substituted with a single o-methoxy, m-methoxy andp-methoxy group. Compounds with 2, 3, 4 or 5 methoxy functions are alsoincluded. Also included a similarly substituted ethoxy, n-propoxy,isoproxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, as well as anyalkoxylated benzene of up to 10 carbon atoms, as a saturated linear orbranched alkyl group, an alkenyl or alkynyl function similar incomposition. As in the instance of methoxy, multiple alkoxy functions onthe benzene ring are also included as is benzyloxy and other aryloxyfunctionalities. It is also anticipated that ketones made from the o-,m-, p-phthalic acids should be useful in the invention. All othersubstituted aromatic ketones the ketone function of which is known to bereactive in typical n-π* photoreduction sequences are included as partof this further embodiment. Typical of these, though not exclusively, isthe list of ketones that can be reduced to pinacols found in Table 7-3of Neckers, D. C. Mechanistic Organic Photochemistry, Reinhold, N.Y.,1967. Halogenated aryl fatty ketones are also possible reactants but, asis well known in the art, these cannot be synthesized by Friedel Craftsreaction chemistry.

Irradiation of Phenones Example 1

In a typical procedure, palmitophenone [C₆H₅C(═O)C₁₆H₃₃] was irradiatedin hexane with a 300 nm artificial light source (UV lamp—Rayonet 350 nmsee table) for a few hours. The gas chromatogram of the reaction mixtureshows mainly two products—acetophenone and 1-tetradecene[CH₂═CH(CH₂)₁₁CH₃] as well as some recovered starting material and asmall amount of side product. The specific procedure, along with thedata, is reproduced below.

Example 2

After a few hours irradiation of stearophenone [C₆H₅C(═O)C₁₈H₃₇] inhexane at 300 nm, the products are acetophenone and 1-hexadecene(CH₂═CH(CH₂)₁₃CH₃. The reactions are almost quantitative in that nearly80% of the reacting phenone is converted to olefin.

The reactions illustrated above rely upon the Norrish II reaction of thearyl alkyl ketone derivative of the fatty acids. In accordance withanother embodiment of the invention, alkyl fatty ketones can bephotodegraded to produce olefins.

Example 3

2-Hexadecanone is the methyl ketone derived from palmitic acid. Whenirradiated at 300 nm in a Rayonet reactor for 7 hours 1-tetradecene andacetone were formed. In contrast to the reaction with the phenones, thereaction with methyl hexadeca-2-one produced a higher yield of sideproduct. This is indicated in the below Table Chemical Yields of NorrishType II Products.

It is an embodiment that fatty acid esters can be photodegraded toproduce olefins by the Norrish II reaction. It is well known in the artthat though esters behave similarly to ketones when they are irradiatedwith light, though the essential process for light absorption in estersdemands a much shorter wavelength of light. In theory the ester functionis more electronically stable than the ketone function, and hence theformer requires more energy for it to be promoted to its excited state.The n-π* transition of esters occurs around 230 nm if the ester isentirely aliphatic (as are all of the esters in methyl soy) while then-π* transition in phenones occurs around 320 nm in the normal,unsubstituted case and the n-π* transition in alkanones occurs at ≈290nm in the normal case.

Example 4

Irradiation of methyl palmitate. Methyl palmitate was dissolved in asmall amount of hexane and irradiated in a quartz container (UV cuvette)at 253.7 nm in the Rayonet reactor. After 7 hours a small amount of1-tetradecene was formed. After 24 hours a larger amount of1-tetradecene and a corresponding isomer (to be identified but likely2-tetradecene (CH₃CH═CHCH₂(CH₂)₉CH₃) was obtained.

Chemical Yields of Norrish Type II Products—

-   -   from 2-hexadecanone p CH₃—(CH₂)₁₃—COCH₃ (in C₆H₆: λ_(max)=284,        ε₂₈₄=22, ε₃₀₀=14)] irradiated at 300 nm for 7 hours, 47.3%        1-tridecene, 2.1% 1-methyl-2-undecylcyclobutanol;    -   from hexadecanophenone[CH₃—(CH₂)₁₄—COC₆H₅ (in C₆H₆: λ_(max)=322,        ε₃₂₂=56, ε₃₀₀=57) irradiated at 350 nm for 7 hours 53.7%        1-tetradecene, 9.3% acetophenone and 3. 3%        1-phenyl-2-tridecylcyclobutanol,    -   from octadecanophenone CH₃—[(CH₂)₁₆—COC₆H₅ (in C₆H₆:        λ_(max)=322, ε₃₂₂=58, ε₃₀₀=61)] irradiated at 350 nm 71.8%        1-hexadecene, 5.7% acetophenone and 3.3%        1-phenyl-2-pentadecylcyclobutanol    -   from methyl palmitate irradiated at 254 nm for 48 hours 20.2%        1-tetradecene and 2% 2-tetradecene.

It is also recognized by those familiar with the art that the aromaticresidue (C₆H₅ is the example cited in examples 1 and 2) may be one of anumber. It should also be recognized, that n-π* configuration of theexcited state formed by the ketone or the ester provides for highreactivity. It should also be recognized by those familiar with thefield that certain ketones may not be highly reactive in thephotoprocesses anticipated because of the so-called effect of orthosubstituted hydrogen donors. Such common functions as ortho-methyl andortho-hydroxy are included in this group in aromatic ketones containingsame are prone to intramolecular hydrogen abstraction from the orthosubstituted function that is unproductive. Though functionalities thatproduce π-π* excited states when in a ketone or ester form may not, apriori be excluded, their reactivity is predicted to be substantiallyless.

The photochemical reactions of fatty acid esters made from alkanolsgenerally require a shorter wavelength light source than do thephotochemical reactions of the corresponding alkanones or phenones.However, once the fatty acids are formed by hydrolysis, conversions toesters other than methyl esters would use alcohols other than methanol.In another embodiment of the invention, by forming esters of the fattyacids containing unsaturated or aromatic functions the absorptionmaximum of the fatty acid function can be shifted to longer wavelengthssuch that the esterified product demonstrates susceptibility to UV-A andUV-B wavelengths. Such preparations are described as well in Wagner, R.B.; Zook, H. B.; Synthetic Organic Chemistry, pp 479 ff, John Wiley &Sons, 1953. Aromatic esters are another photoreactive species that canbe used in accordance with other embodiments of the invention.

Another method involves irradiation of the fatty acid methyl esters withUV-C light. Methyl soy or other essential fatty acid products can beused, in the process directly. However other esters may also besusceptible to UV-A and UV-B wavelengths and such esters are included asbeing preferable. The photodecomposition of esters can be sensitized bylight absorbing species that form excited states having higher energiesthan those of the esters while being, themselves, unreactive and thismitigates the requirement for short wavelength source somewhat. This isa particular possibility when palmitic, stearic, oleic, linoleic andlinolenic esters are prepared from phenols and other such compoundscontaining aromatic groups. This is because the excited state energiesof phenyl esters (both singlet state energies and triplet stateenergies) as well as those of esters of disubstituted phenols, (o-, m,and p-), cresols and the like as palmitates, oleates, stearates,linoleates and linoleneates, lie below those of aliphatic fatty acidesters. Thus, it is anticipated that the reaction of phenyl palmitateproduces 1-tetradecene just as the reaction of methyl palmitate does,but do so more quickly and efficiently. And the sensitized reactions ofboth would be expected to be even faster still. Specific sensitzers thatwould function in this instance would include all those with singletstate and triplet state energies higher than phenyl palmitate. A tableof such energies can be found in any standard book on photochemistry butone that is particularly useful in this context is that by Murov, S. L;Carmichael, I; Hug, G. L Handbook of Photochemistry 2^(nd) ed. New York,1993. Though the excited state energy of fatty acid esters such asphenyl palmitate, phenyl stearate, phenyl oleate, phenyl linoleate andphenyl linolenate have not been measured, it can be anticipated that thetriplet energies, in all likelihood the reactive state, would be ≈300kJ/mol. In particular it would be expected that acetophenone orpropiophenone might therefore be acceptable photosensitizers as wouldbenzoic acid and a number of its derivatives, benzonitrile and a numberof its derivatives, certain phenols, some anilines, benzimidazole,certain pyridines, benzene and a number of substituted benzenes such asthose containing fluorine substituents, phenyl acetic acid, phenylpropionoic acid and even methyl acrylate, methyl methyl acrylate as wellas polymers derived therefrom, and the like. Of course it is recognizedby those familiar with the art that the sensitizer itself should beunreactive under the conditions in which is used for sensitization andthus would be carefully chosen. It should also be recognized that thesensitizer must not react elsewise with the target except as, in thecase of phenyl palmitate, it must absorb at more convenient wavelengthsthan does the acceptor target and must otherwise make the chemicalprocesses faster, cleaner and more convenient than they might otherwisebe. In the sensitized reaction of methyl palmitate for instance, asensitizer absorbing light at longer wavelength than the absorptionmaximum of methyl palmitate might be expected to transfer the energytherein derived if it were in a solution containing a higherconcentration of methyl palmitate than sensitizer. This would have theeffect of producing the same excited state derived from methyl palmitateby direct light absorption. It should be recognized that the list ofsensitizers above is representative, and not exhaustive. Many othercompounds can, and likely will, sensitize the target Norrish Type IIdecomposition processes. Of course it is implied that what is describedfor methyl and phenyl palmitate is also implied for esters of stearic,oleic, linoleic and linolenic acids as well as esters from any naturallyobtained fatty acid found in soy, corn, sunflower, peanut, coconut,palm, cotton, canola and the like. Norrish Type II reactions are alsoreported for polymeric esters including ethylene glycolpolyterephthalate (Gueris, C.; Meybeck, J.; Bull. Soc. Chim. France1972, 2320) and di-n-butyl terephthalate (Day, M.; Wiles, D. M; Can. J.Chem. 1971 49 2916). Accordingly, polymeric esters derived from fattyacids represent additional embodiments of the invention.

Two other practical facts will also be recognized by those familiar withthe art. First only artificial light sources will be of sufficientlyshort wavelength to cause photodegradation of esters. One cannot usesunlight for the direct irradiation at the shorter wavelengths. In theinstance of the sensitized process, however, one will be able to uselonger wavelength sources. And the solvent systems and containers (ifthere are any) used when esters are irradiated must be transparent toshort wavelength radiation. One cannot use a glass apparatus, forexample, nor can one anything but an aliphatic hydrocarbon solvent. Inthe case of methyl soy, one might consider irradiating biodiesel itselfwith short wavelength light. Of course it is also recognized by thosefamiliar with the art that the solutions to be irradiated must,themselves, be transparent. It does not work to use crude materialsparticularly if those crude materials contain dark or off-colorimpurities. Of course it will also be recognized by those familiar fieldthat the successful experimental profile is derived if one measures theultraviolet absorption spectrum of the prospective photochemicalreactant and tailors the output of the light source used for theirradiation to wavelengths identical, or nearly so, with the absorptionmaximum of the prospective photoreactant.

It will be recognized by those familiar with the art that there are manypoints of modification of which the examples are indicative. As theexamples illustrate, one can vary the fatty ketone derived from thenatural oil as either aromatic or aliphatic and one can also vary thefunctional group. Fatty acid amides such as those prepared from thefatty acid of one of its activated derivatives with ammonia or aminesare also photoreactive and undergo Norrish Type II degradations. Theamides may be alkyl amides, (Mellier, D.; Pete, J. P.; Portella, C. Tet.Letters 1971, 47 4559) benzamides (Coyle, J. D.; Kingston, D. H Tet.Letters 1976, 49 4525.) α-oxoamides (Aoyama, H.; Sakamoto, M.; Kuwabara,K.; Yoshida, K.; Omote, Y. J. Amer. Chem. Soc. 1983, 105 1958) andnylons (Do, C. H.; Pearce, E. M.; Bulkin, B. J.; Reimschuessel, H. K; J.Polym Sci, Part A. Polymer Chemistry, 1987, 25 2301) all of which aresusceptible to Norrish Type II processes.

Having described the invention in detail and by reference to specificembodiments thereof, it will be apparent that numerous variations andmodifications are possible without departing from the scope of theinvention as defined by the following claims.

APPENDIX 1 Scope of the Norrish Type II Reaction

The photochemical reactions aromatic ketones are known to undergo aresummarized below.

The Norrish Type II reaction (lowest above) is a split of the ketone toa lower molecular weight ketone and a terminal olefin having an alkylchain that is one less than that found in the starting ketone. Thusbutyrophenone, from butyric acid (alkyl chain not counting the carbon ofthe carboxylic acid, C-3) produces ethylene and valerophenone (alkylchain not counting the carbon of the carboxylic acid, C-4) propylene.The enol tautomerizes to a derivative otherwise known as an acetophenonein the case of phenyl ketones or more generally to an aryl ketone in thecase of substituted aromatic ketones. The syntheses of aryl ketones bythe procedures described below for the purposes outlined in thisspecification is also an embodiment of this invention. There arenumerous reviews discussing Norrish Type II processes including that byScaiano, J. C., Accts. Chem. Res., 1982 15, 252.

One skilled in the art will recognize that the number of carbon atoms inthe alkyl function must be sufficient so that they can be branched andthat the number of carbons in the alkenyl function should be sufficientso that they can accommodate a double bond.

One skilled in the art will also recognize that though the specificationabove identifies alkenes with just one double bond, that 2, 3, 4 or moredouble bonds might also be part of the alkenyl chain and that eachadditional double bond reduces the counted number of hydrogen atoms by 2[C_(m)H_(2m−1) to C_(m)H_(2m−3) C_(m)H_(2m−) C_(m)H_(2m−7) etc.] thoughone skilled in the art will also recognize that the larger the number ofdouble bonds becomes, the more inherently unstable the compound.Likewise, the number of cycloalkyl rings can be greater than the singlering so identified and the number of triple bonds in the linear orbranched array greater than 1 as well. In the latter case one mightanticipate [C_(m)H_(2m−3), C_(m)H_(2m−5), C_(m)H_(2m−7) etc.].

It also is anticipated that one skilled in the art would recognize thatR_(n) could be polymeric as in the case of poly(styrene),poly(ethylene), poly(tetrafluoroethylene) etc.

The alkyl group in the photoreactive ketone, above, can be any of thegroups cited in paragraph [0012] or as otherwise discussed herein exceptthat it must contain a minimum of three carbons the third from theketone or ester function (above) having at least one hydrogen. ThusAryl-C(═O)CR₈R₉CR₁₀R₁₁CHR₁₂R₁₃ in which R₈-R₁₃ may be any of the alkyl,alkyenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl, aryl and thelike cited above with the alkyl group derived from the previouslyidentified fatty acids, palmitic and stearic (also lauric and caprilic)being preferred. Alkenyl functions as in oleic, linoleic and linolenicacid are also preferred.

The groups cited herein are best viewed in the following graphicformulae (Chem 1—general ‘phenone’ formula, Chem 2—specificpalmitophenone and stearophenones, Chem 3—generic alkanone formula)wherein the substituents as cited above are specifically incorporated.

Light suitable for the purpose of Norrish Type II reactions thatspecifically activates the aryl ketones (so-called phenones in the casewhere aryl is phenyl) is in the mid-range UV region of the spectrum, theso-called UV A region. This ranges from 300 nm to 400 nm and somewhatbeyond into the visible region of the spectrum. The actual wavelengthswill depend on the specific functionalized fatty acid derivative and inparticular on the aromatic component of the compound being specificallypredicted by the absorption spectrum of the ketone or derivative and itsexcited state (Jablonski) diagram. The Norrish Type II reaction isgeneral and many, many specific possibilities are thereby incorporatedherein. Specifically, as in CHEM 1, the light may be absorbed by phenyland substituted phenyl with these being preferred but also by naphthyl,anthryl, phenanthryl, and substituted naphthyl, anthryl, phenanthrylCHEM 4 with these likely being excluded because the excited statesformed therefrom may be non-reactive in the subsequent excited stateprocess. This is clear to those familiar with the art as described inTurro, Modern Molecular Photochemistry, Mill Valley, Calif., 1991.

Light of somewhat shorter wavelength can be used to degrade aliphatic[CR₁₄R₁₅R₁₆C(═O)CR₁₇R₁₈R_(19])] ketones which can also be made fromfatty acids by a variety of different methods (Wagner, R. B.; Zook, H.B. Synthetic Organic Chemistry, Wiley, New York 1965 and incorporatedherein for reference). The essential reaction is shown below for thelowest molecular weight ketone for which the Norrish Type II reaction isa possibility, 2-pentanone. Note the olefin formed by the degradation(not shown) must be ethylene. As above, the alkyl group can be any ofsuch groups discussed herein and, as in the case of the phenone, it mustcontain a minimum of three carbons the third from the ketone functionhaving at least one hydrogen.

The Norrish Type II reaction follows a similar course with aliphaticketones (CHEM 3) though the mechanism is somewhat different. Since thelight required for the photodegradation of alkanones is also shorter inwavelength it is anticipated that secondary processes including mostspecifically olefin isomerization might be observed and these areincorporated herein. For example, 2-hexanone CH₃C(═O)C₄H₉ when properlyexposed to light produces acetone CH₃C(═O)CH₃ and propylene (+otherproducts) while 2-heptanone CH₃C(═O)C₅H₁₁ produces 1-butene andacetone+other products. The wavelengths of light needed for thesereactions are in the so-called UV-B region with specific wavelengths ofmaximum absorption used for it ranging from about 275 nm to 300 nm forthe typical aliphatic ketone. Aliphatic aldehydes are similarlyreactive. Hexanal C₅H₁₁C(═O)H produces acetaldehyde CH₃C(═O)H and1-butene; heptanal C₆H₁₃C(═O)H yields acetaldehyde and 1-pentene. Itwill be widely recognized that the possibilities for the photochemicaldegradation of aliphatic ketones as well as of aliphatic aldehydes is,similarly, very large. An early review is that by Wagner, P. J. Acct.Chem. Res. 1971, 4, 168 incorporated herein for reference.

The ester functionality CHEM 5 differs from the ketone functionality byan additional oxygen atom. Methyl hepanoate, for example, has thechemical structure CH₃C(═O)C₆H₁₃. Esters absorb light at much shorterwavelengths than ketones or aldehydes. The light required to degradeesters is in the deep UV-B region ranging from 220 to 250 nm orthereabouts. The products of the Norrish Type II reaction are the same.Methyl hexanoate (methyl ester of hexanoic acid) produces methyl acetate(CH₃C(═O)CH₃ and 1-pentene. Methyl heptanoate CH₃C(═O)C₇H₁₅ (methylester of heptanoic acid) produces methyl acetate and 1-hexene. Thesereactions, because they use deep UV radiation, often produce sideproducts and the olefins produced are likely able to isomerize. Forexample 1-pentene (CH₂═CHCH₂CH₂CH₃) may be accompanied by 2-pentene(CH₃CH═CHCH₂CH₃) and 1-hexene CH₂═CHCH₂CH₂CH₂CH₃ by 2-hexeneCH₃CH═CHCH₂CH₂CH₃ and 3-hexene CH₃CH₂CH═CHCH₂CH₃. But the principleproducts are the same and these isomerization processes an advantage.For photoreactions of carboxylic acid derivatives, see Coyle, J. D.,Chemical Reviews, 1978, 78, 97.

It is widely recognized by those skilled in the art that esters resultfrom reaction of acids (or their derivatives) with alcohols as in thecase of the methanol used to form methyl soy, or phenols as would be thecase of the formation of phenyl palmitate, stearate, oleate, linoleate,linolenate and the like. The general ester formula CHEM 4 identifies thefunctionality. In the case of an alcohol, R₁₄-R₁₆ are H, alkyl, alkenyl,cycloalkyl or alkynyl as defined above. In the case of an aromatic esterR₁₄-R₁₆ are the groups commonly identified as aromatic groups in typicalorganic chemistry textbooks such as Noller, op. cit.

The reaction as generally identified in the case of esters is shown inCHEM 5.

If one or more of the groups (R₁₄-R₁₆, CHEM 5) is aromatic, it may be aphenyl that may be unsubstituted, mono-, di-, and tri-substitutedphenyl, aryl, C₆H_(5-n)R_(n) where R_(n)═R₁,R₂, R₃. R₄,R₅ which are thesame or different. R_(n) may be H, linear or branched alkyl[C_(m)H_(2m+1) where m=1-25], alkenyl [C_(m)H_(2m−1) where m=1-25]cycloalkyl [C_(m)H_(2m−1) where m=1-25], alkynyl [C_(m)H_(2m−3) wherem=1-25], hydroxy, ether [O—R₆ where R₆ is linear or branched alkyl[C_(m)H_(2m+1) where m=1-25], alkenyl [C_(m)H_(2m−1) where m=1-25],cycloalkyl [C_(m)H_(2m−1) where m=1-25], alkynyl [C_(m)H_(2m−3) wherem=1-25], thiophenol, thioether [S—R₆ where R₆ is linear or branchedalkyl [C_(m)H_(2m+1) where m=1-25], cycloalkyl [C_(m)H_(2m−1) wherem=1-25] alkenyl [C_(m)H_(2m−1) where m=1-25], cycloalkyl [C_(m)H_(2m−1)where m=1-25] alkynyl [C_(m)H_(2m−3) where m=1-25], amino [NR₆R₇ whereR₆ and R₇ are the same or different and are H or linear or branchedalkyl [C_(m)H_(2m+1) where m=1-25], cycloalkyl [C_(m)H_(2m−1) wherem=1-25] alkenyl [C_(m)H_(2m−1) where m=1-25], alkynyl [C_(m)H_(2m−3)where m=1-25], piperidino, morpholino, pyrryl, C1-C6 chloroalkyl, C1-C6fluoroalkyl, one or more phenyl or benzyl groups optionally substituted,one or more heterocyclic groups that may or may be alkylated includingthiophene, furan, indole, benzo[b]thiophene, benzo[c]thiophene,benzo[b]furan, benzo[c]furan, indole, heterocyclic groups with two ormore heteroatoms, and the like. The group might also consist ofsubstituent(s) (C1-C4)alkyl, acryloxy, methacryloxy, chloro and fluoro.

One skilled in the art will also recognize that though the specificationabove identifies alkenes with just one double bond, that 2, 3, 4 or moredouble bonds might also be part of the alkenyl chain and that eachadditional double bond reduces the counted number of hydrogen atoms by 2[C_(m)H_(2m−1) to C_(m)H_(2m−3) C_(m)H_(2m−) C_(m)H_(2m−7) etc.] thoughone skilled in the art will also recognize that the larger the number ofdouble bonds becomes, the more inherently unstable the compound.Likewise, the number of cycloalkyl rings can be greater than the singlering so identified and the number of triple bonds in the linear orbranched array greater than 1 as well. In the latter case one mightanticipate [C_(m)H_(2m−3), C_(m)H_(2m−7), C_(m)H_(2m−7) etc.].

It also is anticipated that one skilled in the art would recognize thatR_(n) could be polymeric as in the case of poly(styrene),poly(ethylene), poly(tetrafluoroethylene) etc.

The alkyl group, above, can be any such groups discussed herein exceptthat it must contain a minimum of three carbons the third from the esterfunction (above) having at least one hydrogen. ThusAryl-C(═O)OCR₈R₉CR₁₀R₁₁CHR₁₂R₁₃ in which R₈-R₁₃ may be any of the alkyl,alkyenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl, aryl and thelike cited above with the alkyl group derived from the previouslyidentified fatty acids, palmitic and stearic (also lauric and caprilic)being preferred. Alkenyl functions as in oleic, linoleic and linolenicacid are also preferred.

It will be widely recognized by those familiar with the art thataromatic esters may be more photoreactive than aliphatic esters in theprocesses of interest (incorporated reference, Anderson, J. C.; Reese,C. B. Tet. Lett 1962, 1-4; subsequent Conrad, P. G. II, Givens, R. S.;Weber, J. F. W.; Kander, K Org Lett 2000 2 1545 ff). This is becausearomatic esters are more absorbing in the UV-A and UV-B regions of thespectrum. The introduction of an aryl group (R₁₄-R₁₆=Aryl CHEM 5) ispreferred. In particular aryl functions with electron donating groupssuch as alkoxy, thioalkoxy, amino and the like are preferred.

R_(y) above is as aryl including phenyl groups that may beunsubstituted, mono-, di-, and tri-substituted, C₆H_(5-n)R_(n) whereR_(n)═R₁, R₂, R₃. R₄, R₅ which are the same or different. R_(n) may beH, linear or branched alkyl [C_(m)H_(2m+1) where m=1-25], alkenyl[C_(m)H_(2m−1) where m=1-25]cycloalkyl [C_(m)H_(2m−1) where m=1-25],alkynyl [C_(m)H_(2m−3) where m=1-25], mono, di, or poly substitutednaphthyl C₁₀H_(8-n)R_(n), mono, di, or poly substituted anthrylC₁₄H_(10-n)R_(n), mono, di or poly substituted phenanthrylC₁₄H_(10-n)R_(n), polycondensed aromatic, C₁₆H₁₀R_(n) and the like;R_(n) may also be hydroxy, ether [O—R₆ where R₆ is linear or branchedalkyl [C_(m)H_(2m+1) where m=1-25], alkenyl [C_(m)H_(2m−1) wherem=1-25], cycloalkyl [C_(m)H_(2m−1) where m=1-25], alkynyl [C_(m)H_(2m−3)where m=1-25], mono-, di-, and tri-substituted, C₆H_(5-n)R_(n), mono,di, or poly substituted naphthyl C₁₀H_(8-n)R_(n), mono, di, or polysubstituted anthryl C₁₄H_(10-n)R_(n), mono, di or poly substitutedphenanthryl C₁₄H_(10-n)R_(n), polycondensed aromatic, C₁₆H₁₀R_(n) andthe like, F, Cl, Br, I, C_(m)H_(2m+2−x)M_(x) where M=F, Cl, Br, I, andx=1-25, thiophenol, thioether [S—R₆ where R₆ is linear or branched alkyl[C_(m)H_(2m+1) where m=1-25], cycloalkyl [C_(m)H_(2m−1) wherem=1-25]alkenyl [C_(m)H_(2m−1) where m=1-25], cycloalkyl [C_(m)H_(2m−1)where m=1-25] alkynyl [C_(m)H_(2m−3) where m=1-25], mono-, di-, andtri-substituted, C₆H_(5-n)R_(n), mono, di, or poly substituted naphthylC₁₀H_(8-n)R_(n), mono, di, or poly substituted anthryl C₁₄H_(10-n)R_(n)mono, di or poly substituted phenanthryl C₁₄H_(10-n)R_(n), polycondensedaromatic, C₁₆H₁₀R_(n) and the like, amino [NR₇R₈ where R₇ and R₈ are thesame or different and are H or linear or branched alkyl [C_(m)H_(2m+1)where m=1-25], cycloalkyl [C_(m)H_(2m−1) where m=1-25] alkenyl[C_(m)H_(2m−1) where m=1-25], alkynyl [C_(m)H_(2m−3) where m=1-25],mono-, di-, and tri-substituted, C₆H_(5-n)R_(n), mono, di, or polysubstituted naphthyl C₁₀H_(8-n)R_(n), mono, di, or poly substitutedanthryl C₁₄H_(10-n)R_(n), mono, di or poly substituted phenanthrylC₁₄H_(10-n)R_(n) polycondensed aromatic, C₁₆H₁₀R_(n) and the like,piperidino, morpholino, pyrryl, ammonium, [NR₄ ⁺], amido [—NR₂C(═O)—],ester, [—COOR_(n)], sulfonamide [—SONR₂], aldehyde —[CHO], ketone[—C(═O)R] one or more heterocyclic groups that may or may not bealkylated including thiophene, furan, indole, benzo[b]thiophene,benzo[c]thiophene, benzo[b]furan, benzo[c]furan, indole, heterocyclicgroups with two or more heteroatoms, and the like. The group might alsoconsist of substituent(s) (C1-C10)alkyl, acryloxy, methacryloxy, chloroand fluoro. R_(n) may also be polymeric including poly(ethylene),poly(isopropenyl), poly(propylene), poly(butadienyl), poly(styryl),poly(acylate), poly(methacrylate), poly(fluorocarbon),poly(chlorocarbon) and the like.

APPENDIX 2 Light Sources

It is also the purpose of the patent to teach that though sunlight maybe used as the source of UV-A, and in part, UV-B if that is necessary,artificial light sources may be preferred. These artificial sourcesinclude commercial light sources like mercury resonance lamps andelectrode-less discharge lamps, as well as light emitting diodes (LED's)that produce either visible or UV light. A partial table of such sourcesis shown below.

Artificial Light Sources Dose, Light Source mW/cm² Comments 395 nm 5 mmLED 57 Inexpensive 5 mm LED PLLS-1 Prototype 49 WPL developed lightsource prototype UVPC Source 132 Commercial source by UV Process Xe-500BLamp 121 Industrial Xe lamp 3M Overhead Proj. 526 Standard overheadprojector 250 PMP UV Lamp 1400 Industrial UV curing lamp EFOS Ultracure594 Commercial blue light source Fusion H-bulb 1346 Popular industrialcuring source THC³ Blue LED 367 Ultrabright 5 mm LED THC³ Green LED 93Ultrabright 5 mm LED THC³ Red LED 144 Ultrabright 5 mm LED LIII R. BlueEmitter 521 High intensity emitter LIII Blue Emitter 328 High intensityemitter LIII Green Emitter 171 High intensity emitter LIII Red Emitter581 High intensity emitter

APPENDIX 3 Uses for Aromatic Byproducts

The aromatic ketone(s) produced in the decomposition reaction, theso-called acetophenones or their congeners have a plethora of uses suchas for termite control

Naphthalene derivatives as termite repellents and termiticides.Henderson, Gregg; Ibrahim, Sanaa A.; Patton, Rosemary; Laine, Roger A.;Zhu, Betty C. R.; Chen, Feng. (USA). U.S. Pat. Appl. Publ. (2005), 25pp. CODEN: USXXCO US 2005037045 A1 20050217 Patent written in English.Application: US 2003-641315 20030814. CAN 142:192781 AN 2005:140565CAPLUS

as drug delivery carriers as in 20040235691

Nonbar personal product compositions comprising crystalline waxstructured benefit agent premix or delivery vehicle Pham, Quynh; (MurrayHill, N.J.); O'Connor, Stephen M.; (New York, N.Y.); Glynn, John R. JR.;(Westfield, N.J.); Lips, Alexander; (Edgewater, N.J.), in the synthesisof electronic materials as in

Synthesis of polyphenylenes from acetylaromatic compounds. Shmakova, O.E.; Khotina, I. A.; Nikonova, S. N.; Rusanov, A. L.; Teplyakov, M. M.Inst. Elementoorg. Soedin. im. Nesmeyanova, Moscow, Russia.Vysokomolekulyarnye Soedineniya, Seriya B: Kratkie Soobshcheniya (1992),34(10), 36-44. CODEN: VYSBAI ISSN: 0507-5483. Journal written inRussian.

Curing of polyphenylenes based on acetylaromatic compounds in thepresence of organosilazanes. Teplyakov, M. M.; Shmakova, O. E.; Khotina,I. A.; Izmailov, B. A.; Rusanov, A. L. Inst. Elementoorg. Soedin. im.Nesmeyanova, Moscow, Russia. Vysokomolekulyarnye Soedineniya, Seriya A(1992), 34(10), 23-30. CODEN: VYSAAF ISSN: 0507-5475. Journal written inRussian. CAN 119:96930 AN 1993:496930 CAPLUS

Polyphenylenes from ketals of acetylaromatic compounds with reactivefurfurylidene and nitrile groups. Korshak, V. V.; Teplyakov, M. M.;Dmitrenko, A. V.; Kakauridze, D. M. Inst. Elementoorg. Soedin., Moscow,USSR. Vysokomolekulyarnye Soedineniya, Seriya A (1980), 22(2), 256-61.CODEN: VYSAAF ISSN: 0507-5475. Journal written in Russian. CAN 92:181933AN 1980: 181933 CAPLUS

Production of Aromatic acetal compound

JP2115140A 1990-04-27JP2600858B2 B2 1997-04-16 And

Preparation of Acetylaromatics from Isopropenyl Compounds. Kondo,Masahiro; Tanaka, Michio; Taniguchi, Katsuo. (Mitsui PetrochemicalIndustries, Ltd., Japan). Jpn. Kokai Tokkyo Koho (1990), 4 pp. CODEN:JKXXAF JP 02115140 A2 19900427 Heisei. Patent written in Japanese.Application: JP 88-267637 19881024. CAN 113:131744 AN 1990:531744 CAPLUS

And as hair restorers

“Hair restorer”. Christen, A. (1926), GB 264862 19260121 Patent languageunavailable. CAN 22:2615 AN 1928:2615 CAPLUS

Methyl ketones, which may be produced by the Norrish Type II reactionalso have many uses including as

Antibotulinal properties of selected aromatic and aliphatic ketones.Bowles, Bobby L.; Miller, Arthur J. East. Reg. Res. Cent., U.S. Dep.Agric., Philadelphia, Pa., USA. Journal of Food Protection (1993),56(9), 795-800. CODEN: JFPRDR ISSN: 0362-028X. Journal written inEnglish. CAN 120:161981 AN 1994:161981 CAPLUS

Analysis of] vanilla extracts and imitations. Ensminger, Luther G. Food& Drug Admin., Los Angeles, Calif., Journal of the Association ofOfficial Agricultural Chemists (1957), 40 423-33. CODEN: JOACAZ ISSN:0095-9111. Journal language unavailable. CAN 51:48670 AN 1957:48670CAPLUS

to make aromatherapy oils such as in the case of, but not limited to thecase of, piperonyl methyl ketone and cedryl methyl ketone. Ketonessynthesized by the Norrish Type II reaction producing such products willbe preferred.

APPENDIX 4 Other Addition Reactions of Hydroperoxides to Olefins

Organic peroxides. XIV. Base catalyzed addition of hydroperoxides onaryl(vinyl)sulfones. Kropf, Heinz; Ball, Michael; Hofmann, Klaus. Inst.Org. Chem. Biochem., Univ. Hamburg, Hamburg, Fed. Rep. Ger. JustusLiebigs Annalen der Chemie (1976), (12), 2316-24.

Organic peroxides. X. Base-catalyzed addition of hydroperoxides tooxiranes. Kropf, H.; Ball, M.; Schroeder, H.; Witte, G. Inst. Org.Chem., Univ. Hamburg, Hamburg, Fed. Rep. Ger. Tetrahedron (1974),30(16), 2943-8.

Dioxododecenoic Acid: A Lipid Hydroperoxide-Derived BifunctionalElectrophile Responsible for Etheno DNA Adduct Formation. Lee, Seon Hwa;Elipe, Maria V. Silva; Arora, Jasbir S.; Blair, Ian A. Center for CancerPharmacology, University of Pennsylvania School of Medicine,Philadelphia, Pa., USA. Chemical Research in Toxicology (2005), 18(3),566-578.

Preparation of Cycloalkanols and Cycloalkanones from CycloalkylHydroperoxides. Hamamoto, Shunichi; Yamanaka, Mitsuo; Nakamura,Takahito; Shimano, Tetsuro. (Ube Industries, Ltd., Japan). Jpn. KokaiTokkyo Koho (1997), 5 pp. CODEN: JKXXAF JP 09077704 A2.

Multidipole effect in addition reactions of oxygen, cumyl hydroperoxide,and cumylperoxy radical to the double bond of pentaerythritolmonoacrylate tripropionate. Sokolov, A. V.; Pliss, E. M.; Denisov, E. T.Inst. Khim. Fiz., Chemogolovka, USSR. Izvestiya Akademii Nauk SSSR,Seriya Khimicheskaya (1988), (2), 293-7.

Formation of hydroperoxides with unconjugated diene systems duringautoxidation and enzymic oxygenation of linoleic acid. Haslbeck, Franz;Grosch, Werner; Firl, Joachim. Dtsch. Forschungsanst. Lebensmittelchem.,TU Muenchen, Garching, Fed. Rep. Ger. Biochimica et Biophysica Acta(1983), 750(1), 185-93.

Reversal of stereospecificity during allylic hydroperoxidation of3-norcarene and bicyclo[4.2.0]oct-3-ene derivatives arising fromstructurally enforced quenching of singlet oxygen by the hydrazidefunctionality. Paquette, Leo A.; Liao, C. C.; Liotta, Dennis C.;Fristad, William E. Evans Chem. Lab., Ohio State Univ., Columbus, Ohio,USA. Journal of the American Chemical Society (1976), 98(20), 6412-13.

Addition of N-acetylcysteine to linoleic acid hydroperoxide. Gardner, H.W.; Weisleder, D.; Kleiman, R. NRRL, ARS, Peoria, Ill., USA. Lipids(1976), 11(2), 127-34.

Addition of hydroperoxides to N-vinyl compounds. Lederer, Michael.Farbwerke Hoechst A.-G., Frankfurt/M.-Hoechst, Fed. Rep. Ger. ChemischeBerichte (1972), 105(7), 2169-74.

In situ olefin-derived peroxides. Effectiveness for initiating radicaladdition and polymerization reactions. Norton, Charles J.; Dormish,Frank L.; Reuter, Michael J.; Seppi, Ned F.; Beazley, Phillip M. DenverRes. Cent., Marathon Oil Co., Littleton, Colo., USA. Industrial &Engineering Chemistry Product Research and Development (1972), 11(1),27-35.

Stereochemistry of the addition of tert-butyl hydroperoxide tocyclopentadiene. Haubenstock, H.; Mennitt, P. G.; Butler, Peter E.Richmond Coll., City Univ. of New York, Staten Island, N.Y., USA.Journal of Organic Chemistry (1970), 35(10), 3208-10.

Addition of tert-butyl hydroperoxide to isoolefins. Antonovskii, V. L.;Emelin, Yu. D. USSR. Editor(s): Emanuel, N. M. Usp. Khim. Org.Perekisnykh Soedin. Autookisleniya, Dokl. Vses. Konf., 3rd (1969),Meeting Date 1965, 310-13. Publisher: Izd. “Khimiya”, Moscow, USSR.

1. A method comprising: providing a natural source of fatty acids orfatty acid derivatives; and irradiating the fatty acid or fatty acidderivatives directly with UV-C light to decompose them into one or morehydrocarbons.
 2. The method of claim 1 wherein the fatty acid or fattyacid derivative is a fatty acid ester, fatty acid amide, or a fattyalkanone.
 3. The method of claim 1 wherein the natural source isvegetable oil or animal fat.
 4. The method of claim 3 wherein thevegetable oil is selected from the group consisting of peanut, soybean,corn, sunflower, safflower, tung, canola, linseed, hemp, coconut,cotton, and mixtures thereof.
 5. The method of claim 1 wherein the fattyacid is selected from the group consisting of palmitic acid, stearicacid, oleic acid, linoleic acid, linolenic acid, and mixtures thereof.6. The method of claim 1 further comprising hydrogenating the fatty acidwhen the fatty acid is an unsaturated fatty acid.
 7. A methodcomprising: providing a natural source of fatty acids or fatty acidderivatives; adding an unreactive, light absorbing specie to the naturalsource of fatty acids or fatty acid derivatives; and irradiating thenatural source and unreactive, light absorbing specie directly with atleast one of UV-A light and UV-B light; wherein the unreactive, lightabsorbing specie transfers energy absorbed thereby immediately afterlight absorption to the fatty acids or fatty acid derivatives todecompose the fatty acids or fatty acid derivatives into one or morehydrocarbons.
 8. The method of claim 7 wherein the fatty acid or fattyacid derivative is a fatty acid ester, fatty acid amide, or fattyalkanone.
 9. The method of claim 7 wherein the natural source is avegetable oil selected from the group consisting of peanut, soybean,corn, sunflower, safflower, tung, canola, linseed, hemp, coconut,cotton, and mixtures thereof, or is animal fat.
 10. The method of claim1 wherein the fatty acid is selected from the group consisting ofpalmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid,and mixtures thereof.
 11. The method of claim 1 further comprisinghydrogenating the fatty acid when the fatty acid is an unsaturated fattyacid.
 12. A method comprising: providing a source of palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid, or combinationsthereof, or derivatives thereof; and irradiating the source directlywith UV-C light; wherein the UV-C light decomposes the palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid, or combinationsthereof, or derivatives thereof into one or more hydrocarbons.
 13. Themethod of claim 12 further comprising hydrogenating any of the fattyacids in the source that are unsaturated fatty acids.
 14. The method ofclaim 12 wherein the source is a natural oil or animal fat.
 15. Themethod of claim 14 wherein the natural oil is a vegetable oil selectedfrom the group consisting of peanut, soybean, corn, sunflower,safflower, tung, canola, linseed, hemp, coconut, cotton, and mixturesthereof.
 16. The method of claim 12 wherein the derivative is an esterof the palmitic acid, stearic acid, oleic acid, linoleic acid, linolenicacid, or combinations thereof.
 17. The method of claim 12 furthercomprising: adding to the source an unreactive, light absorbing speciethat absorbs radiation of at least one of UV-A and UV-B wavelengths; andirradiating with at least one of UV-A light and UV-B light instead ofUV-C light.
 18. The method of claim 17 further comprising hydrogenatingany of the fatty acids in the source that are unsaturated fatty acids.19. The method of claim 17 wherein the source is a vegetable oilselected from the group consisting of peanut, soybean, corn, sunflower,safflower, tung, canola, linseed, hemp, coconut, cotton, and mixturesthereof, or is animal fat.
 20. The method of claim 17 wherein thederivative is an ester of the palmitic acid, stearic acid, oleic acid,linoleic acid, linolenic acid, or combinations thereof.